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H?.\ 


UNIVERSITY  OF  ILLINOIS 


May. ..24 198I- 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

Alden. . Geo  rge, . . .Lewi  3 

entitled  -The. ..Hy.&r.olys ia... of... Aromatic... Sulphonic. -Ac-ids- 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF.. Ba.chelo.r*...oT..Sc.lence-in.....Cheinlat-r.y.. 


<a±L 

Instructor  in  Charge 


Approved  : 


HEAD  OF  DEPARTMENT  OF. 


-Li  C •Ljs  'CJ1 


ACKNOWLEDGEMENT. 

The  author  wishes  to  express  his  appreciation 
to  Dr.  C.S.  Marvel  under  whose  supervision  this  work  was 
carried  on,  for  the  helpful  suggestions  made  during  the 
course  of  this  investigation  and  in  the  writing  of  this 
thesis. 


TABLE  OF  CONTENTS 


page. 


I 

Introduction. 

1 

II 

History. 

2 

III 

Theoretical  Part. 

5 

IV 

Experimental  Part. 

10 

Apparatus . 

10 

Prep,  of  Compounds. 

10 

Data. 

19 

V 

Summary. 

21 

VI 

Bibliography. 

23 

1 


The  Hydrolysis  of  the  Aromatic  Sulphonic  Acids. 

I.  Introduction 

Altho  the  problem  of  hydrolyzing  aromatic  sulphonic 
acids  to  the  hydrocarbons  is  not  a new  one,  nevertheless,  it 
has  never  been  studied  in  a systematic  manner.  The  author's 
work  was  mainly  to  study  the  effect  of  the  number  of  groups 
in  the  ring,  position,  kind  of  groups  and  catalyzers  on  the 
amount  and  rate  of  hydrolysis.  Along  the  same  line  of  work 
the  various  temperatures  of  hydrolysis  were  determined  which 
suggests  the  possibility  of  a separation  of  various  aromatic 
compounds  by  fractional  hydrolysis  of  their  sulphonic  acids. 


71 


II  History. 

Freund  (l)  in  1861  found  that  on  dry  distilling 
benzene  sulphonic  acid  he  obtained  a product  that  had  a 
strong  odor  and  a large  refractive  index.  This  compound 
he  called  benzene.  He  believed  either  one  of  two  things 
happened. 


Later  in  1855  Beilstien  (2)  used  a method  of  dry 
distillation  for  the  recovery  of  xylene  from  its  sulphonic 
acid  and  later  in  1878  Jacobson  (3)  used  a similar  method 
to  recover  metaxylene  from  its  sulphonic  acid. 

Armstrong  (4)  in  1878  separated  mesitylene  and 
pseudocumene  by  heating  their  sulphonic  acids  at  100°with 
muriatic  acid  whereby  the  mesitylene  sulphonic  acid  is  alone 
hydrolyzed;  the  pseud omene  is  recovered  by  heating  at 

o o 

130  - 140.  It  was  long  known  that  mesitylene  could  be 
separated  from  its  sulphonic  acid  by  mere  steam  distillation. 
The  same  author  in  1883  applied  these  methods  to  the  tetra- 
methyl  benzenes. 

Miller  and  Armstrong  (5)  did  the  first  real  work 
on  the  subject  and  used  the  method  that  was  used  in  this 
work.  The  method  consisted  in  passing  the  steam  thru  a hot 


. 

' •.  ,*  n ; 


concentrated  acid  solution  until  hydrolysis  takes  place. 

They  stated  that  the  rate  of  hydrolysis  does  not  depend  on 
the  excess  of  sulphuric  acid  but  that  the  sulphuric  acid 
is  necessary  to  obtain  a high  temperature.  They  experienced 
no  difficulty  in  separating  calcium  and  barium  salts  by 
their  methods.  They  stated  that  the  sources  of  error  are: 


(a)  Thru  dissolution  of  a small  quantity 

in  water. 

(b)  Thru  incomplete  separation  of  hydrocarbon. 

(c)  Thru  evaporation  of  hydrocarbon. 

They  tabulated  the  hydrolysis  points  of  benzene. 


toluene,  ortho,  meta  and  paraxylenes  sulphonic  acids,  etc., 
and  suggested  the  possibility  of  separating  various  hydro- 
carbons by  fractional  hydrolysis  of  their  sulphonic  acids 
but  state  that  this  is  almost  impossible  because  hydrolysis 
is  generally  carried  out  at  a temperature  higher  than  the 
critical  hydrolysis  temperature.  They  also  did  considerable 
work  with  the  hydrolysis  of  sulphonic  acids  in  sealed  tubes 
and  found  that  the  temperatures  of  hydrolysis  were  very 
different  under  these  conditions. 


Kelbe  (6)  in  1886  improved  the  Miller  and  Armstrong 


method  .somewhat  by  passing  steam  thru  a heated  copper  tube 
before  passing  it  thru  the  solution.  The  advantages  are 
that  a large  excess  of  sulphuric  acid  is  avoided  and  also 
that  ortho  brom  toluene  and  ortho  brom  xylene  prepared  by 


this  method  seemed  to  be  more  stable  toward  oxidizing  agents 
than  those  prepared  by  other  methods. 


■ 

' 


><' 


4 


Jacobson  (7)  in  1887  found  that  when  sodium 
pentamethylbenzenesulphonate  is  shaken  with  concentrated 
sulphuric  acid  and  light  petroleum, hydrolysis  occurs  and 
the  hydrocarbon  is  obtained  on  evaporation  showing  the 
effect  of  a number  of  groups  in  the  ring  on  hydrolysis. 

Later  Friedel  and  Craft  (8)  used  aluminum  chloride 
and  phosphoric  acid  to  bring  about  the  hydrolysis  of  the 
aromatic  sulphonic  acids  and  obtained  good  results;  the 
yields  in  the  relatively  few  cases  tried  were  greater  than 
those  with  sulphuric  acid.  In  the  present  work  it  was 
found  that  almost  invariably  with  phosphoric  acid  the  yield 
is  about  the  same  or  greater  than  the  yield  with  sulphuric 
acid  as  a catalyst. 

Fournier  (9)  in  1892  used  Friedel  and  Craft  methods 
to  obtain  diethyl  benzene  from  diethyl  benzene  sulphonic 
acid  with  almost  theoretical  results. 

Later  in  1901  J.M.  Craft  (IQ)  studied  the  rate 
of  hydrolysis  of  sulphonates;  chiefly  metaxylene  sulphonate 
for  10  - 35/£  of  hydrochloric  acid  heated  in  sealed  tubes 

o 

at  100.  The  amount  of  hydrolysis  was  noted  for  different 
amounts  of  hydrochloric  acid  and  the  velocity  of  reaction 
was  found  to  be  proportional  to  the  concentration  of  the 
catalytic  agent.  With  an  increase  of  6 % in  concentration 
there  is  a velocity  four  times  as  great.  Craft  does  not 
fully  understand  the  reason  for  this  phenomena. 


' 


5 


III  Theoretical 


Most  of  the  previous  writers  have  mentioned  the 
fact  that  benzene  sulphonie  acid  can  be  hydrolyzed  almast 
quantitatively  but  these  results  could  not  be  duplicated. 

When  we  introduce  an  (OH)  group  in  the  benzene 
ring  the  ortho  and  para  hydrogens  are  greatly  activated 
and  hydrolysis  seems  to  take  place  easier.  Thus  para  phenol 
sulphonie  acid  hydrolyzes  very  easily;  the  rate  being 
greater  with  phosphoric  acid  as  a catalyzer  than  with  sul- 
phuric acid  as  a catalyzer. 

They  yield  of  napthalene  from  alpha  and  beta 
napthalene  sulphonie  acids  are  almost  theoretical  using 
sulphuric  acid  a3  a catalyzer.  With  phosphoric  acid  as  a 
catalyzer  the  rate  of  hydrolysis  is  faster  and  the  yield 
is  about  the  same.  The  alpha  napthalene  sulphonie  acid 
comes  over  fcapidly  at  first  and  suddenly  stops  which  seems 
to  indicate  that  the  sulphonie  acid  group  is  split  off  and 

r^SUT  phrvrm  t.pg  in  t.Viia  ‘h<a+.a  nnalt.lnn 


The  yield  with  phosphoric  acid  is  greater  with 
the  alpha  than  with  the  beta  napthalene  sulphonie  acid. 

When  the  (OH)  group  is  introduced  into  the  napthalene 


rings  in  the  beta  position  the  hydrolysis  is  decreased. 

Bender  (11)  found  a method  of  preparing  napthol  (1)  sulphonie 
acid  (2)  and  stated  that  it  hydrolyzed  readily  with  sulphuric 


I 

■ 


. 


* ■ 


m 


6 


acid  with  theoretical  results.  From  this  we  would  believe 
that  when  the  sulphonic  acid  group  is  in  the  alpha  position 
it  splits  off  and  rearranges  itself  in  the  beta  position 
before  hydrolyzing.  This  is  almost  impossible  because  of 
the  fact  that  the  (OH)  group  is  in  the  beta  position  and 
therefore  the  hydrolysis  would  be  low.  In  the  case  where 
the  sulphonic  acid  group  is  in  the  beta  position  hydrolysis 
is  rapid. 

H 

w KaJ 

N&f\tholfe)  Solfihon/r  /\ciq/0)  N&/ithol(lJ  Sulphonic  /\ci(jfc) 

The  amount  of  hydrolsis  of  napthol  (2)  sulphonic  acid  (1) 
with  sulphuric  acid  and  phosphoric  acid  as  catalyzers  is 
about  the  same. 

The  ortho,  raeta  and  para  toluene  sulphonic  acids 
were  then  studied  in  order  to  give  us  an  idea  as  to  the 
effect  of  position  in  the  ring  relative  to  the  time  and 
amount  of  hydrolysis.  With  sulphuric  acid  as  a catalyzer 
we  found  that  the  ortho  toluene  sulphonic  acid  hydrolyzes 
and  that  the  meta  and  para  toluene  sulphonic  acids  do  not 
showing  that  position  In  the  ring  does  have  an  effect. 

With  phosphoric  acid  as  a catalyzer  we  found  that  the  para 
toluene  sulphonic  acid  hydrolyzes  easier  than  the  ortho 
toluene  sulphonic  acid  so  we  can  see  that  the  catalyzer  has 


an  effect  on  the  rate  of  hydrolysis  as  well  as  the  position 
of  the  ring  has  an  effect  on  the  rate  of  hydrolysis.  If 
conclusions  are  to  be  drawn  from  a series  of  experiments  of 


f 


. ' 

» 

this  nature  the  same  catalyzers  must  be  used  through  out. 

The  para  chloro,  para  bromo  and  para  iodo  benzene 
sulphonic  acids  were  next  studied  with  a view  of  seeing 
whether  or  not  the  weight  of  the  group  in  the  ring  had 
anything  to  do  with  the  amount  and  time  of  hydrolysis. 

With  sulphuric  acid  as  a catalyzer  we  have  for  chloro 
benzene  sulphonic  acid  12%  hydrolysis,  for  bromo  benzene 
sulphonic  acid  37 % hydrolysis  and  for  iodo  benzene  sulphonic 
acid  56%  hydrolysis  showing  that  as  the  molecular  weight 
increases  the  amount  of  hydrolysis  increases.  With  phos- 
phoric acid  as  a catalyzer  this  is  also  true  but  the  rate 
and  amount  of  hydrolysis  are  considerably  greater.  In  the 
case  of  chloro  benzene  sulphonic  acid  the  hydrolysis  is 
just  four  times  as  great  and  the  time  of  hydrolysis  is 
shorter.  In  each  case  phosphoric  acid  is  a better  catalyzer 
of  the  two.  This  may  be  because  with  an  excess  of  sulphuric 
acid  there  is  a greater  tendency  to  resulphonate.  In  all 
the  causes  mentioned  we  can  see  that  the  kind  of  group  has 
an  effect  on  hydrolysis  and  also  that  with  increasing  mole- 
cular weight  the  amount  is  greater. 

The  sodium  meta  nitro  benzene  sulphonate  was 
found  to  act  very  differently  from  other  sulphonates  studied. 
The  distillate  from  the  hydrolysis  with  sulphuric  acid  was 
of  a yellow  color  and  the  residue  in  the  flask  was  mainly 
carbon  showing  that  the  molecule  was  destroyed.  The  distillate 
contained  no  nitro  benzene  and  did  not  give  a test  for  nitric 
acid.  Phosphoric  acid  was  tried  with  no  better  results. 


8 


Evidently  the  nitro  compounds  decompose  very  differently  from 
the  other  sulphonic  acids  studied. 

Jacob 3 on  (7)  found  that  the  pent a methyl  benzene 
sulphonic  acid  decomposed  on  mere  shaking  with  sulphuric 
acid.  With  these  facts  in  mind  it  was  thought  that  increas- 
ing the  weight  of  an  aliphatic  side  chain  might  have  an 
analogous  effect.  With  these  compounds  however  the  increase 
of  hydrolysis  does  not  exactly  follow  the  rule.  We  notice 
that  the  para  toluene  sulphonic  acid  does  not  hydrolyze 
with  sulphuric  acid  as  a catalyzer.  The  ethyl  benzene  and 

secondary  butyl  benzene  sulphonic  acids  do  hydrolyze  showing 
that  an  increase  in  the  weight  of  the  molecule  increases 
the  amount  of  hydrolysis.  With  the  use  of  phosphoric  acid 
as  a catalyzer  the  yields  are  practically  doubled  showing 
that  phosphoric  acid  is  a better  catalyzer. 

With  lauryl  benzene  sulphonic  acid  the  heat 
generated,  by  the  addition  of  sulphuric  acid  to  the  water 
solution  was  sufficient  to  hydrolyze  the  sulphonic  acid. 

^e  can  see  from  this  the  effect  of  the  weight  of  the 

group  or  groups  in  the  ring  on  the  amount  and  time  of 
hydrolysis.  Sodium  |>ara  chloro  benzene  sulphonate  was 
then  hydrolyzed  and  the  introduction  of  another  group  in 
the  ring  had  a marked  effect  on  the  amount  of  hydrolysis, 
the  hydrolysis  with  both  sulphuric  acid  and  phosphoric 
acid  as  catalyzers  being  about  Q0%, 

With  the  use  of  sodium  ortho  dichloro  benzene 
sulphonate  we  have  a similar  reaction,  the  hydrolysis  with 


. 


' 


» 


b 


9 


sulphuric  acid  being  about  65$.  In  this  case  the  hydrolysis 
with  sulphuric  acid  is  greater  than  with  phosphoric  acid 
as  a catalyzer.  Similarly  with  ortho  xylene  sulphonic  acid 
we  have  tho  same  effect  of  additional  groups  in  the  ring 
although  the  yield  is  not  the  3ame  as  the  yield  with  the 
sodium  ortho  dichloro  benzene  sulphonate. 

It  has  long  been  known  that  camphor  when  steam 
distilled  in  the  presence  of  a dehydrating  agent  gave 
cymene.  It  was  found  that  in  a similar  manner  camphor 

sulphonic  acid  breaks  dov/n  to  cymene  very  readily. 


Sodium  benzyl  sulphonate  was  studied  to  see  what 
effect  hydrolysis  would  have  on  an  aliphatic  hydrocarbon 
in  comparison  with  an  aromatic  hydrocarbon.  Sulphuric  acid 
and  phosphoric  acid  were  both  used  as  catalyzers  but  with 
negative  results. 

In  the  preparation  of  lauryl  benzene  by  the 
Friedel  and  Craft  reaction  an  intermediate  compound 
perhaps  dodecylene,  was  isolated.  It  gave  the  bromine  test 
for  unsaturation  and  its  boiling  point  and  specific  gravity 
was  like  that  of  dodecylene.  This  may  be  evidence  in 

favor  of  the  theory  that  the  first  steps  in  the  ordinary 
Friedel  and  Craft  reaction  is  a splitting  out  of  the 
halogen  acid  from  the  alkyl  halide. 


. 


fei 


IV  Experimental. 


in 


Apparatus . 

The  apparatus  used  was  a simple  steam  distillation 
apparatus.  The  distilling  flask  was  connected  to  an  air 

condenser  which  in  turn  was  connected  to  a water  condenser. 

All  the  connections  leading  into  the  flask  were  made  of 
pyrex  tubing  and  because  of  the  high  temperatures  of  hydrolysis 
the  thermometer  was  incased  in  a pyrex  tub? which  was  filled 
with  cotton  seed  oil.  This  precaution  was  taken  to  prevent 
the  thermometer  from  being  broken  and  to  prevent  the  numbers 
on  the  thermometer  from  being  effaced. 

Preparation  of  Compounds. 

The  following  compounds  were  already  prepared 

and  therefore  there  is  no  need  of  discussing  their  methods 
of  preparation:  sodium  benzene  sulphonate,  sodium  beta 

napthalene  sulphonate,  sodium  para  brom  benzene  sulphonate, 
sodium  meta  nitro  benzene  sulphonate,  sodium  para  chlor 
toluene  sulphonate,  sodium  ortho  dichloro  benzene  sulphonate, 
sodium  ortho  xylene  sulphonate,  methyl  ether  of  carvocrol 
sulphonic  acid  and  camphor  sulphonic  acid. 

Sodium  alpha  napthalene  sulphonate:-  This  com- 
pound was  prepared  affic&rding  to  the  method  of  Barnett  (12) 
which  will  not  be  described  here.  It  was  found  that  when 
the  alpha  napthalene  sulphonic  acid  was  boiled  with  water 


* 


11 


to  remove  the  napthalene  that  a considerable  amount  was 
hydrolyzed  and  it  was  almost  impossible  to  obtain  a product 
uncontaminated  with  napthalene.  Sodium  carbonate  was  added 
to  the  solution  and  it  was  found  that  the  sodium  salt  was 
relatively  stable  to  boiling  with  water  so  that  in  this 
manner  the  compound  could  be  easily  purified. 

Para  phenol  sul phonic  acid:-  This  compound  was 
prepared  according  to  Vanino  (21).  Two  hundred  (200)  grams 
of  phenol  was  melted  at  35°  - 40°  , 100  grams  of  fuming 

sulphuric  acid  was  added  care  being  taken  that  the  temp- 
erature does  not  rise  too  high.  This  mixture  was  heated 
slightly  and  allowed  to  stand  for  about  twenty-four  hours. 
The  two  layers  gradually  disappeared  and  on  standing  the 
sulphonic  acid  crystallised  out.  The  slight  excess  of 
sulphuric  acid  was  not  removed  because  it  was  not  necessary 
for  the  experiment. 

Sodium  napthol  (2)  sulphonate  (l):-  To  about 
40  grams  of  b-napthol  about  100  c.c.  of  sulphuric  acid 
(mixture  of  *1%  fuming  sulphuric  acid  and  concentrated 
sulphuric  acid)  was  added  and  the  whole  mass  heated  on 
an  oil  bath  to  160°  until  the  two  layers  disappeared. 

The  excessof  sulphuric  acid  was  neutralized  with  barium 
hydroxide,  the  barium  sulphate  filtered  off  and  the  filtrate 
added  to  a saturated  sodium  chloride  solution.  The  yield 
was  poor,  about  9 grams. 

Sodium  ortho  toluene  sulphonate:—  Several  methods 
were  tried  in  the  preparation  of  sodium  ortho  toluene  sul- 


phonate.  The  amide  of  0-toluene  sul phonic  acid  was  refluxed 
for  several  hours  with  a sodium  carbonate  solution  but  with 
little  success. 

The  method  of  hydrolysis  described  in  Winther  (13) 
which  uses  chlorsulphonic  acid  was  tried.  This  method 

consists  in  heating  the  amide  with  chlorsulphonic  acid  for 

several  hours  at  130  - 150^  extracting  with  ether  and 

hydrolyzing  with  sodiu$  carbonate.  The  reaction  did  not 

work. 

Finally  a mixture  of  ortho  and  para  toluene 
sulphonyl  chlorides  were  separated  by  vacuum  distillation 
as  used  by  Majert  and  Ebers  (14).  About  thirty  parts  in 
a hundred  were  distilled  over  giving  us  the  ortho  compound 
and  by  a series  of  vacuum  distillations  the  ortho  compound 
was  obtained  pure.  This  sulphonyl  chloride  was  hydrolyzed 
by  refluxing  with  a saturated  sodium  carbonate  solution 
with  almost  theoretical  results. 

Sodium  meta  toluene  sul phonate:-  This  compound 
was  prepared  according  to  the  method  of  Metcalf  (15)  and 

Griffin  (16).  To  100  grams  of  para  toluidine  was  added 
200  grams  of  7%  fuming  sulphuric  acid.  This  mass  was 

heated  until  fumes  of  sulphur  dioxide  came  off  and  the 
mixture  kept  at  180  for  an  hour.  After  cooling  the  mixture 
was  Poured  into  twice  its  volume  of  water  and  a dark  pasty 
mass  resulted  consisting  mainly  of  the  meta  and  ortho 
sul phonic  acids  of  para  toluidine.  The  remaining  sulphuric 
acid  was  precipitated  by  an  excess  of  barium  hydroxide, 
the  solution  boiled  to  remove  any  unchanged  toluidine  and 


. . ' ■> --*?**  If 


13 


the  barium  sulphate  filtered  off.  On  cooling  the  long  sulphur 
yellow  needles  crystallized  out.  This  was  filtered  off  and 
the  ortho  and  meta  sul phonic  acids  we re  separated  by  difference 
of  solubility  ina  potassium  hydroxide  solution.  The  para 
toluidine  meta  sulphonic  acid  is  insoluble  while  the  para 
toluidine  ortho  sulphonic  acid  is  soluble  in  the  potassium 
hydroxide  solution. 

Twenty-five  (25)  grams  of  the  potassium  para 
toluidine  meta  sulphonate  was  suspended  in  a 150  G,c.  of  a 
92%>  solution  of  alcohol  to  which  hydrochloric  acid  had  been 
added.  This  was  placedin  an  ice  bath  and  when  the  temp- 
erature was  at  0° sodium  nitrite  was  added  and  the  temperature 

O 

gradually  allowed  to  rise  up  to  46  until  the  reaction  was 
complete,  which  requires  about  30  minutes.  The  pinkish 
white  crystals  were  filtered  off  by  a filter  pump  and  washed 
with  alcohol. 

Twenty  (20)  grams  of  this  diazo  compound  was 
decomposed  in  200  c.c.  of  absolute  methyl  alcohol  to  which 

9 grams  of  dried  sodium  carbonate  had  been  added.  This 

0 

reaction  was  carried  on  at  0 and  the  solution  gradually 

O 

warmed  to  30.  This  solution  was  allowed  to  stand  over 
night  and  then  heated  to  35.  The  alcohol  was  distilled 
off  and  the  resulting  mixture  was  so  contaminated  with 
sodium  chloride  that  it  was  almost  impossible  to  obtain  a 
pure  product. 


Instead  of  sodium  nitrite,  amyl  nitrite  was  used 
with  better  results,  because  a sodium  salt  was  not  formed. 


...... 


14 


This  method  is  practically  the  same  except  that  the  diazo 

compound  was  prepared  and  decomposed  in  the  same  alcoholic 

from 

suspension.  The  yield  was  poorM i about  25  grams  of  the 
potassium  para  toluidine  meta  sulphonate  only  6 grams  of 
the  dark  impure  potassium  meta  toluene  sulphonate  resulted. 

Sodium  para  toluene  sulphonate:-  This  compound 
was  prepared  by  refluxing  para  toluene  sulphonyl  chloride 
with  a saturated  sodium  carbonate  solution  for  about  an 
hour.  The  reaction  goes  very  easily  and  the  yield  is 
almost  quantitative. 

Sodium  para  chi or  benzene  sulphonate:-  This 
compound  was  prepared  by  the  same  method  as  used  by 
Langmuir  (17)  in  preparing  sodium  para  iodo  benzene  sul- 
phonate. 60  c.c.  of  chlor  benzene  was  heated  with  120  c.c. 
of  an  equal  mixture  of  7%  fuming  sulphuric  acid  and 
concentrated  sulphuric  acid  on  an  oil  bath  for  several 
hours  or  until  the  two  layers  had  disappeared.  This 
solution  was  added  to  the  same  amount  of  water  and  finally 
when  cooled  poured  into  a saturated  sodium  chloride  sol- 
ution. The  sodium  para  chlor  benzene  sulphonate  was 
filtered  off  by  suction.  The  yield  was  good,  about  70  grams. 

Sodium  para  iodo  benzene  sulphonate:-  This 
compound  was  prepared  by  the  previous  mentioned  method  of 
Langmuir.  From  50  grams  of  iodo  benzene,  35  grams  of  the 
sodium  para  iodo  benzene  sulphonate  was  obtained. 

Sodium  para  ethyl  benzene  sulphonate:-  To  50  c.c. 
of  ethyl  benzene  100  c.c.  of  a mixture  of  7 % fuming  sulphuric 


* 


' 


. 


15 


acid,  and  concentrated  sulphuric  acid  was  added  and  the 
mixture  heated  gently  on  a steam  cone  until  the  two  layers 
mixed;  allowed  to  stand  several  hours  and  added  to  100  c.c. 
of  water.  The  excess  of  acid  was  neutralized  with  sodium 
carbonate  and  then  the  mass  was  added  to  a saturated 
sodium  chloride  solution.  The  sodium  salt  crystallized 
out  in  beautiful  leaflets;  yield  about  35  grams. 

Secondary  Butyl  benzene:-  Two  runs  were  made 
in  the  preparation  of  this  compound.  In  the  first  run 
45  c.c.  of  normal  butyl  bromide  and  140  c.c.  of  benzene 
were  dried  over  calcium  chloride  and  then  refluxed  with 
20  grams  of  aluminum  chloride  for  about  three-fourths  of 
an  hour.  The  mass  was  then  poured  into  water.  The  two 
layers  were  separated  and  the  benzene  extraction  dried 
over  calcium  chloride  for  about  four  hours.  The  benzene 
was  distilled  off  and  the  remainder  was  fractionated; 
the  fraction  boiling  at  172°-  176° at  atmospheric  pressure. 
The  yield  was  34  grams. 

In  the  second  run  50  c.c.  of  normal  butyl  bromide, 
200  c.c.  of  benzene  and  20  grams  of  aluminum  chloride  were 
used.  The  yield  was  35  grams. 

This  reaction  according  to  Schram  (18)  who  used 
normal  butyl  chloride  instead  of  normal  butyl  bromide . gives 
the  secondary  butyl  benzene.  The  boiling  point  of  the 

Q O 

compound  (173  - 175)  and  the  specific  gravity  (0.865)  found, 
corresponded  to  that  for  secondary  butyl  benzene. 


Sodium  secondary  butyl  benzene  sulphonate:- 


• 

‘ 

. 


- . . 

_ 


16 


34  grams  of  secondary  butyl  benzene,  50  c.c.  sf  concentrated 
sulphuric  acid  and  20  c.c.  of  7$  fuming  sulphuric  acid  were 
allowed  to  stand  dor  several  hours  in  the  cold  but  there 
was  no  reaction.  The  mass  was  then  heated  on  a steam  cone 
for  several  hours  until  the  two  layers  disappeared.  The 
excess  of  acid  was  neutralized  with  sodium  carbonate  and 
the  resulting  mixture  added  to  a saturated  sodium  chloride 
solution.  The  yield  of  the  sodium  salt  was  15  grams. 

Lauryl  bromide:-  This  compound  was  prepared 
according  to  the  method  of  Kamm  and  Marvel  (19).  In  a 
250  c.c.  round  bottom  flask  40  grams  of  lauryl  alcohol, 

85  grams  of  hydrobromic  acid  (34$)  and  42  c.c.  of  sulphuric 
acid  were  refluxed  for  about  three  hours.  The  solution 
was  diluted  with  water,  the  bromide  separated  by  difference 
of  specific  gravities  and  then  washed  with  sulphuric  acid, 
water  and  dilute  sodium  carbonate  solution  successively. 

The  bromide  was  extracted  with  ether.  The  ether  was  then 
evaporated  off  and  the  product  distilled  under  a vacuum 

O o 

of  about  40  mm.,  the  bromide  coming  over  at  196  - 200. 

The  yield  was  30  grams  or  about  55$  of  the  theory. 
Undoubtedly  the  low  yield  is  due  to  the  fact  that  a 34$ 
solution  of  hydrobromic  acid  was  used  while  the  directions 
call  for  a 48$  solution. 

Lauryl  benzene:-  The  reaction  of  Priedel  and 
Craft  was  used  in  the  preparation  of  this  compound. 

29  grams  of  lauryl  bromide,  250  c.c.  of  benzene  and  25  grams 
of  aluminum  chloride  were  refluxed  for  four  hours.  The 


. 


' 


1 


17 


resulting  solution  was  poured  into  water  and  the  two  layers 
separated.  The  benzene  lawyer  was  dried  over  calcium  chloride 
over  night,  benzene  was  distilled  off  and  the  remainder 
distilled  under  a vacuum  of  46  mm.  Two  fractions  were 
collected,  the  boiling  point  of  the  first  fraction  was 

o © 

100  - 110  and  the  yield  was  8.50  grams,  while  the  second 
was  190°-  197° and  the  yield  Was  10  grams.  The  first  fraction 
is  perhaps  dodecylene  because  is  gave  a positive  test  for 
unsaturation  and  the  specific  gravity  was  almost  that  of 
dodecylene,  while  the  second  fraction  is  undoubtedly  lauryl 
benzene.  The  specific  gravity  of  lauryl  benzene  was  found 
to  be  0.9225  at  20° and  its  boiling  point  190°-  197°at  46  mm. 
pressure.  In  odor  and  general  appearance  lauryl  benzene 
resembles  the  higher  aliphatic  hydrocarbons. 

Sodium  lauryl  benzene  sulphonate :-  To  7 grams 
of  lauryl  benzene  20  c.c.  of  concentrated  sulphuric  acid 
and  10  c.c.  of  7%  fuming  sulphuric  acid  were  added. 

This  mixture  was  occasionally  shaken  and  sulphonated  very 
readily  in  the  cold.  It  was  poured  in  a similar  amount 
of  water,  the  excess  of  acid  neutralized  the  sodium  car- 
bonate and  finally  added  to  a saturated  sodium  chloride 
solution  where  the  sodium  salt  crystallized  out.  The  yield 
was  very  poor;  about  2 grams.  This  poop  yield  may  be 
explained  by  the  fact  that  hydrolysis  took  place  when  it 
was  poured  into  water. 

Sodium  benzyl  sulphonate:-  The  potassium  salt 
of  this  compound  was  first  prepared  by  Bflhler  (20),  by 


V 


i 


' 

refluxing  benzyl  chloride  with  potassium  sulfite.  To  100  grams 
of  benzyl  chloride  a solution  containing  125  grams  of  sodium 
sulfite  was  added  and  this  mixture  refluxed  for  about  five 
hours.  When  the  reaction  was  finished  there  remained  an  oil 
which  had  a boiling  point  of  190° and  ifc  evidently  benzyl 

alcohol.  On  cooling  the  solution  the  sodium  benzyl  sulphonate 
crystallized  out  in  beautiful  leaflets.  The  yield  is  85 

grams  or  about  45^  of  theory.  The  yield  of  benzyl  alcohol 

was  40  c.c. 

In  figuring  the  yields  in  the  following  data 
the  author  in  each  case  endeavoured  to  prepare  the  mono 

sulphonic  acid  and  all  the  yields  are  figured  approximately 
on  this  basis. 


. 


I ' 


. 


. 


DATA  (Continued) 


Sodium  para 

secondary  buty! 

5 

50  c.c.  HaS04 

170-195 

°l/3 

0.64 

23 

benzene  sul- 

10 

" fl  h3pq, 

170-210 

1/2 

2.58 

47 

phonate. 

Sodium  lauryl 

Hydro 

lyzes  almost  quar 

titativ 

ely  on 

additl 

on 

benzene  sul- 

of  sulphuric 

acid. 

phonate . 

Sodium  para 

10 

35  c.c.  H,  S0„ 

200-220 

i W 

4.81 

87 

chlor  toluene 

10 

It  tt  ^ TT  ^ 

TI  II 

2.14 

40 

sulphonate. 

10 

50  " H3P0y 

240-280 

3/4 

4.23 

77 

Sodium  ortho 

10 

25  c.c.  HdS0v 

240-280 

3/4 

4.00 

66 

dichloro  ben- 

10 

ti  n ti 

TI  fl 

ti 

ti 

it 

zene  sul phonal 

e 10 

" M H3P0, 

260-320 

35  mir 

.3.30 

55 

Sodium  ortho 

10 

25  c.c.  H,  S0V 

160-130 

1 , 

1.88 

45 

xylene  sulphon- 

10 

Tt  If  tl 

150-180 

3/4 

1.54 

35 

ate . 

Methyl  ether  of 

10 

25  cnc.  H §0, 

IfiO-lJJO 

25  mir 

.3.86 

50 

carvocrol  sul- 

6 

ti 

2.18 

52 

phonic  acid. 

Camphor  sulphon- 

10 

25  c.c.  HaS04 

160-170 

1/2 

2.40 

25 

ic  acid. 

10 

50  " H3P04 

160-180 

it 

3.90 

40 

Sodium  benzyl 

10 

25  c.c.  HaSOw 

160-210 

1 

__ 

sulphonate. 

10 

40  ” H3POv 

it  ti 

it 

— 

- 

Sodium  para 

10 

25  c.c.  H.SOu 

200-210 

1 

2.98 

45 

bromo  benzene 

10 

25  " 

200-240 

1 

3.72 

57 

sulphonate . 

10 

25  c.c.  H3P0* 

220-240 

1/4 

4.10 

62 

' 


21 


V SUMMARY. 

I The  following  compounds  were  prepared  and  the  amount,  tine 

and  temperatures  of  hydrolysis  studied:  Sodium  benzene 

sulphonate,  Fara  phenol  sulphonic  acid,  Sodium  beta 
napthalene  sulphonate,  Sodium  alpha  napthalene  sul- 
phonate, Sodium  napthol  (2)  sulphonate  (1),  Sodium 
ortho  toluene  sulphonate,  Sodium  meta  toluene  sulphon- 
ate, Sodium  para  toluene  sulphonate,  Sodium  para 
chloro  benzene  sulphonate,  Sodium  para  bromo  benzene 
sulphonate,  Sodium  para  iodo  benzene  sulphonate, 

Sodium  meta  nitro  benzene  sulphonate,  Sodium  para 
ethyl  benzene  sulphonate.  Sodium  para  secondary 
butyl  benzene  sulphonate,  Sodium  lauryl  benzene 
sulphonate,  Sodium  para  chlor  toluene  sulphonate, 

Sodium  ortho  dichloro  benzene  sulphonate,  Sodium 
ortho  xylene  sulphonate,  Methyl  ether  of*  carvocrol 
sulphonic  acid.  Camphor  sulphonic  acid,  and  Sodium 
benzyl  sulphonate. 

II  It  has  been  shown  that  the  time  and  amount  of  hydrolysis 

of  aromatic  sulphonic  acids  depends  on: 

(a)  Kind  of  groups  in  ring. 

(b)  Number  of  groups  in  ring. 

(c)  Position  of  groups  in  ring. 

III  Phosphoric  acid  was  used  as  a catalyzer  and  in  many 

cases  was  superior  to  sulphuric  acid  as  a catalyzer. 


22 


IV  Sodium  benzyl  suLphonate  was  found  to  act  very  differently 

from  the  other  compounds  studied  showing  the  charact- 
eristics of  the  aliphatic  compounds. 

V Lauryl  benzene  has  been  prepared  and  its  physical 

constants  determined.  It  was  shown  that  it  sulphon- 
ates  very  readily  but  that  the  sulphonic  acid  was 
relatively  unstable. 


, 


23 


VI  BIBLIOGRAPHY. 

1.  Annalen  120:80  (1861) 

2.  " 133:36  (1865* 

3.  Ber.  11:19  (1878) 

4.  Ber.  11:1697  (1878) 

5.  J.  Chem.  Soe.  45:148  (1884) 

6.  Ber.  19:92  (1886) 

7.  Ber.  20:900  (1387) 

3.  Comptes  Rendus  109:95  (1909) 

9.  Bulletin  de  la  Societie  Chemie  (3)  7:652  (1892) 

10.  Ber.  34:1350  (1901) 

11.  Ber.  22:994  (1889) 

12.  Barnett  "Preparation  of  Organic  Compounds”  232  (1912) 

13.  D.  R.  P.  105870 

14.  D.  R.  P.  95338  or  Ber.  38:730  (1905) 

15.  J.  Chem.  Soc.  15:301  (1893) 

16.  " " n 19:183  (1897) 

17.  Ber.  28:91  (1895) 

18.  Monatsheft  9:620  (1898) 

19.  J.  Am.  Soc.  42 : Feb.  (1920) 

20.  Annalen  154:50  (1870) 

21.  Vanino  "Organic  Chemistry"  p.  611  (1914) 


